1,3,5-tris-(2{40 -hydroxy-benzoyl)-benzenes

ABSTRACT

1,3,5-tris-(2&#39;&#39;-hydroxy-benzoyl)-benzenes are stabilizers for organic material. The compounds are obtained through dealkylating of the corresponding ethers.

United States Patent [72] inventors Hansjorg Heller, Dornliyegi Biehen/BS,

3115f JSWiitzIeilaiiid 211 AppLNo. 878,871 22 Filed NOV.2l, 1969 45 Patented Dec. 14,1971

[54] l,3,5-TRlS-(2 HYDROXY-BENZOYL)-BENZENES 9 Claims, No Drawings 52 us. Cl 260/591, 260/4595, 260/3985, 117/33.3, 106/196 424 59 [51] Int. Cl ..C07c 49/80, CO7c 49/82 [50] Field of Search 260/591 [56] References Cited UNITED STATES PATENTS 3,113,121 12/1963 Hoch etal. 260/866 Primary Examiner-Daniel D. Horwitz Attorneys-Karl F. Jorda and Martin J. Spellman ABSTRACT: 1,3,5-tris-(2 hydroxy-benzoyl)-benzenes are stabilizers for organic material. The compounds are obtained through dealkylating of the corresponding ethers.

1 ,3 ,S-TRIS-(Z '-I'IYDROXY-BENZOYL)-BENZENES DESCRIPTION OF THE INVENTION The present invention relates to new l,3,5-tris-(2'-hydroxybenzoyU-benzenes, to their use as protective agents against light rays, e.g. as a constituent of light-ray filters or for the stabilizing of light-sensitive organic material, to processes for the production of the new compounds and, as an industrial wherein X represents hydrogen, hydroxyl, alkoxy having one to 22 carbon atoms, alkenyloxy having three to 18 carbon atoms, or benzyloxy which can be substituted by alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms or by chlorine, are good protective agents against light rays.

Alkoxy groups, which are denoted in the formula I by X, are, e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy, amyloxy, hexoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy or docosyloxy groups, whereby the alkyl groups can be branched and straight. As alkenyloxy group, X represents, e.g. the A- or A -propenyloxy group of the A -heptadecenyloxy group. If a benzyloxy group X 'is further substituted by alkyl or alkoxy, it can be a question of methyl, ethyl, propyl, butyl, tert.butyl, methoxy, ethoxy, propoxy or butoxy substitutents.

In compounds of the general formula I, which are particularly suitable as protective agents against light rays, X represents the hydroxyl group, alkoxy group having one to 22 carbon atoms, alkenyloxy group having three and four carbon atoms such as, e.g. A or A -propenyloxy or methallyloxy groups, or the benzyloxy group.

Of the compounds of the formula I which are particularly suitable, those compounds are preferred wherein X denotes hydroxyl, alkoxy having one to 22 carbon atoms or alkenyloxy having three and four carbon atoms.

Particularly preferred are compounds of the formula I wherein X represents alkoxy having four to 12 carbon atoms such as the butoxy, amyloxy, hexoxy, octoxy, decyloxy or dodecyloxy groups.

Compared with similar, previously known protective agents against light rays, the new compounds of the formula I are characterized by a low degree of inherent color, improved fastness to sublimation, better fastness to light and better compatibility with the substrates. As protective agents against light rays, the new compounds of the formula I are, therefore, particularly suitable for substrates which are further processed at high temperature.

The new compounds of the formula I are introduced into the light-sensitive carriers or into the light filters in amounts of 0.0] to 30 percent. The amount to be added of the new compounds is governed, amongst other factors, by the thickness of the light filters being produced. For very thin layers, e.g. in the case of lacquer coatings, amounts of l to percent are preferred but for thick layers such as, e. g. in polymethacrylate sheets, amounts of 0.01 to 1 percent are preferred.

Suitable as carrier materials for the new compounds of the formula I are primarily organic polymers, both thermoplastic polymers and curable synthetic resins (thcrmosetting polymers). Thereby applicable are fully synthetic polymers and also natural polymers as well as their polymerhomologous chemical modification products. Appropriate amongst the fully synthetic polymers are pure addition polymers and pure condensation polymers, but also condensation polymers cross-linked by addition polymerization.

The addition polymers coming into consideration as carrier materials for the new protective agents against light rays, can be classified under the following main types:

I. Homopolymers and copolymers of vinyland vinylidenemonomers, which are converted by radical, ionic or metal-or ganic polymerization initiators into the corresponding polymers. Examples of such monomers, the polymerisates of which are suitable as carrier materials are:

Polymerizable, ethylenic, unsaturated halogenated hydrocarbon compounds such as, e.g. vinyl chloride, vinyl fluoride and vinylidene chloride,

polymerizable hydrocarbons with double bonds capable of addition such as, e.g. styrene, isobutylene, ethylene, propylene, l-butene, B-methyl-l-butene and 4-methyl-lpentene, whereby both the atactic and the tactic polymerisates apply,

afi-unsaturated polymerizable carboxylic acids and their functional derivatives such as acrylic acid, methacrylic acid, acrylonitrile, alkyl esters and amides of acrylic and methacrylic acid, e.g. the methyl, ethyl and butyl esters of methacrylic acid and acrylic acid,

polymerizable acyl derivatives of ethylenic unsaturated alcohols and amines, whereby are suitable acyl radicals of alkaneand alkene-carboxylic acids having up to 18 carbon atoms and of aromatic monocyclic carboxylic acids, such as benzoic acids and phthalic acids, as well as acyl radicals of cyclic carbonic acid imides such as, e.g. those of cyanuric acid. Examples are: allyl phthalate, polyallyl melamines, vinyl acetate, vinyl stearate, vinyl benzoate and vinyl maleate, polymerizable polyenes with conjugated double bonds such as butadiene, isoprene, chloroprene, sorbic acid and esters thereof.

2. Homoand copolymers of epoxides which are obtained by acidor base-catalytic thermosetting. Suitable in this class are, e.g. the polymerisates of the bisglycidyl ethers of the geminal bis-( P-hydroxyphenyl)-alkanes and cycloalkanes.

3. Homopolymers and copolymers of lactams and lactones such as, e.g. the polymerisates of e-caprolactam or lauryllactam.

4. Homopolymers and copolymers of aldehydes such as, e.g. of formaldehyde and acetaldehyde, such as the polyoxymethylene and the polyoxyethylene.

5. Reaction products of isocyanates with hydroxyl and/or amino compounds such as, e.g. those of dior polyisocyanates with bivalent or polyvalent hydroxyl or amino compounds. Belonging to this class are also the polyurethanes and polyureas which are obtained by reaction of diisocyanates with polyesters and/or polyethers containing hydroxyl groups.

The condensation polymers suitable as carrier materials for the new compounds of the formula I are, amongst others, polyesters and polyamides. To be mentioned in this respect are linear thermoplastic polyand copolycondensates, which are derived from dicarboxylic acids and organic dihydroxy derivatives or organic diamines, on the one hand, and from hydroxy or aminocarboxylic acid on the other hand. Linear polycondensates are, e.g. the fibre-forming polymers of (0,0)- dicarboxylic acids and w,w'-dihydroxy compounds or (0,0)- diamines as well as of w-hydroxycarboxylic acids or of waminocarboxylic acids, which are derived from saturated aliphatic, cycloaliphatic and carbocyclic nonanellated aromatic carboxylic acids.

Suitable for the production of linear condensation products are, e.g. the following components: adipic acid-hexamethylenediamine, sebacic acid-hexamethylenediamine, adipic acid/sebacic acid-hexamethylenediamine, terephthalic acid-ethylene glycol, terephthalic acid-1,4-dimethylolcyclohexane, IO-amino-decanecarboxylic acid.

Cross-linked polycondensates as carrier materials are hotthermosetting and are obtained, in particular, by condensation of aldehydes with polyvalent condensable compounds. Mention is made of formaldehyde condensates with phenols, ureas and melamines.

Of the condensation polymers cross-linked by subsequent addition polymerization are the polyester resins. These are polycondensates from at least one unsaturated organic dicarboxylic acid with polyvalent alcohols, which can be modified with saturated and/or aromatic dicarboxylic acids or their anhydrides and which can be cross-linked by addition of compounds having double bonds capable of addition. Suitable, for example, as unsaturated dicarboxylic acids are: maleic acid or its anhydride, itaconic acid, citraconic acid or fumaric acid; suitable as saturated dicarboxylic acids are the succinic, adipic, azelaic or sebacinic acids, as aromatic dicarboxylic acids the isophthalic acid or the anhydrides of the phthalic, tetrachlorophthalic or tetrabromophthalic acids and l,2,3,4,7,7-hexachlorodicyclo-(2,2,l )-hept-2-ene-5,6-dicarboxylic acid anhydride; suitable as alcohols are ethylene, propylene, diethylene, neopentyl glycol or trimethylpentanediol, and suitable as cross-linking agents are styrene, pchlorostyrene, diallylphthalate, methylmethacrylate, vinyl toluene or diallylcyanurate.

The natural polymers, suitable as carrier materials for the new protective agents against light rays, are e.g. polysaccharides, such as cellulose or also rubber and proteins.

Amongst the polymer-homologous, chemically modified synthetic polymers are, e.g. the reaction products of polyvinyl alcohols with aldehydes such as polyvinyl butyral, and the saponification products of polyvinyl esters. Polymerhomologous, chemically modified natural polymers, as carrier materials for the new protective agents against light rays are, e.g. the cellulose esters and cellulose ethers, such as the cellulose esters of the acetic acid, propionic acid, benzoic acid with, on average, one to three acyl groups per unit of glucose.

The above listed polymers can also be used in the form of mixtures, as carriers of the new protective agents against light rays in the compositions according to the invention.

Particularly valuable compositions, according to the invention, contain, as carriers of the new protective agents against light rays, light-sensitive polymerisates which are derived from styrene, vinyl chloride, 'vinyl fluoride, acrylonitrile, olefins, acrylic acid esters and/r methacrylic acid esters, as well as polyesters, polyamidcs, polyester resins, polyacetals, polycarbonates, polyurethanes, cellulose ethers and cellulose esters. Especially preferred carriers are polymeric hydrocarbons such as, e.g. highand low-pressure polyethylene, polypropylene, polybutene, poly(-3-methyl-l-butene), poly (4-methyl-l-pentene), ethylene-butene copolymers, ethylene-propylene copolymers, ethylene-propylene-terpolymers, propyleneethylene-polyallomers.

Also suitable as carriers, in addition to these polymers, are natural as well as synthetic light-sensitive waxes, fats and oils, and also complex systems such as photographical material, emulsions containing light-sensitive fatty substances, emulsions or dispersions of the aforementioned polymers.

The molecular weight of the aforestated polymers is of secondary importance, providing that it is within the limiting values required for the characteristic mechanical properties of the polymers concerned. Depending on the polymers, it can be 1000 to several millions.

The incorporating of the new compounds into these polymers is effected, e.g., depending on the nature of the polymers, by the introducing of at least one of these compounds, and optionally further additives, into the melt, according to methods normally applied in practice, before or during moulding, or by dissolving them in the corresponding monomer before polymerization, or by dissolving of the polymer and/or the additives in solvents and subsequent evaporation of the latter.

Further additives are, e.g.:

Antioxidising agents such as 2,2'-thiobis-( 4-methyl-6-tert.butylphenol 4,4 '-thiobis-( 3- rnethyl-6-tert.-butylphenol); 2,2'methylene-bis-(4-methyl-6- tert.butylphenol); 2,2-methylene-bis-(4-ethyl-6-tert.butylphenol 4,4-methylene-bis-( 2-methyl-6-tert.butylphenol 4,4-butylidene-bis-( 3-methyl-6-tert.butylphenol 2,2 methylene-bis-[4-methyl-6-(a-methylcyclohexyl)-phenol1; 2,6-di-(2'-hydroxy-3-tert.butyl-5'-methylbenzyl)-4- methylphenol; l,l ,3-tris-( 4'-hydroxy-2'-methyl-5 '-tert.butylphenyl)-butane; l,3,5-trimethyl-2,4,6-tri-(3',5'-ditert.butyl-4-hydroxybenzyl)-benzene; esters of the B-4-hydroxy-3,5- ditert.butylphenyl-propionic acid with monoor polyvalent alcohols such as methanol, octadecanol, hexanediol, trimethylolethane or pentaerythrite; v2,4-bis-octylmercapto45- (4-hydroxy-3,5-ditert.butylanilino)-s-triazine; 2,4-bis-(4- hydroxy-3,S-ditertbutylphenoxy)-6-octylmercapto-s-triazine; l l-bis-( 4-( 4'-hydroxy-2-methyl-5 '-tert.butyl)-phenyl-3- dodecylmercapto-butane; 4-hydroxy-3,5-ditert. butylbenzylphosphonic acid ester such as the diethylor dioctadecylester; (3-methyl-4-hydroxy-5-tert. butylbenzyl)-malonic aciddioctadecyl ester; S-( 3 ,5-dimethyl-4-hydroxybenzyl thioglycolic acid octadecyl ester; phenyl-l-naphthylamine; phenyl-2-naphthylamine; N,N'-diphenyl-p-phenylenediamine; N,N'-di-2-naphthyl-p-phenylenediamine; N,N-di-sec.butyl-pphenylenediamine; 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; 6-dodecyl-2,2,4-trimethyl-l ,2-dihydroquinoline; mono-,

and dioctyliminodibenzyl; polymerized 2,2,4-trimethyl-l,2- dihydroquinoline.

UV-absorbers and protective agents against light rays such as 2-(2'-hydroxyphenyl)benzotriazoles, e.g. the 5-methyl-, 3,5' -ditert.butyl-, 5-tert.butyl-, 5-chloro-3,5'-ditert.butyl-, 5- chloro-3tert.butyl-5-methyl-, 3,5'-ditert.amyl-, 3'-methyl-5 '-B-carbomethoxyethyl-, 5-chloro-3 ,5 '-ditert.amyl-derivative; 2,4-bis-( 2'-hydroxyphenyl)-6-alkyl-s-triazines such as the 6-ethylor G-undecyl-derivative; 2-hydroxy-benzophenones such as the 4-hydroXy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4- dodecyloxy-, 4,2',4-tri-hydroxyor 2'-hydroxy-4,4'- dimethoxy-derivative; phenylsalicylate; octylphenyl-salicylate; benzoylrecorcin; dibenzoylresorcin; a-cyano-B-B- diphenylacrylic acid ethylor isoctyl ester; a-carbomethoxycinnamic acid methyl ester; a-cyano-B-methyl-p-methoxycinnarnic acid methylor butyl ester; N-(B-cyano-B-carbomethoxy-vinyl)-2-methyl-indoline; nickel complexes of the 2,2'-thiobis-(4-ditert.octylphenol), such as the 1:1 and 2:1 complex, optionally with other ligands such as n-butylamine; nickel dibutyl-dithiocarbamate; nickel salts of 4-hydroxy-3,5- di-tert. butylbenzylphosphonic acid monoalkyl esters such as the methyl, ethyl, or butyl ester, the nickel complex of the 2- hydroxy-4-methylacetophenoneoxime; 4,4-dioctyloxyaxanilide; 2,2-di-octyloxy-5,5'-ditert.butyloxanilide; 2,2'-didodecyloxy-5,5'-ditert.butyloxanilide.

Metal deactivating agents such as monoand dihydrazides of monobasic and polybasic acids such as oxalic, adipic, salicylic, terephthalic or isophthalic acid; substituted oxamides and oxanilides; N-salicyloyl-salicylaldehyde-hydrazones; n-butylbenzotriazole; tetrahydrobenzotriazole; 2- guanidinobenzoimidazole.

Nucleating agents such as 4-tert.butylbenzoic acid, adipic acid, diphenylacetic acid. Peroxide decomposing compounds such as esters of the B-thiodipropionic acid, e.g. the lauryl, stearyl, myristyl or tridecyl ester; salts of the 2mercaptobenzoimidazole, e.g. the zinc salt; diphenylthio-urea; triphenyl phosphite; diphenylalkyl phosphites: phenyldialkyl phosphites; trinonylphenyl phosphite; trilauryl phosphite; trioctadecyl phosphite; 3,9-diisodecyloxy-2,4,8,lO-tetraoxa-3,9- diphosphaspiro-( 5 ,5 )-undecane; tri-( 4-hydroxy-3 ,5-ditert.butylphenyl)-phosphite.

Other stabilizers such as potassium, barium, cadmium, mag nesium, calcium or zinc salts of organic acids, e.g., stearates or laurates; basic or neutral lead salts of organic or inorganic acids; tin-containing stabilizers such as dibutyl tin laurates, maleates or -mercaptides; hexamethylphosphoric acid triamide; copper salts such as' copper acetates or copper lor copper ll-halides, optionally in combination with alkali halides, ihydrophosphites, phosphites and phosphates or free phosphorous or phosphoric acid; manganese ll-salts such as the chloride, hypophosphite or phosphate, optionally in combination with other hypophosphites, phosphites and phosphates; dicyanodiamide; diphenylurea.

Other additives such as softeners, antistatics, flameproofing agents, pigments, soot.

inorganic fillers such as, e.g., asbestos, glass fibers, kaolin, talcum.

The new protective agents against light rays can also be applied to polymer granulate and to thinner carrier structures, such as to films or threads, from baths, e.g., from aqueous dispersions or from solution in organic solvents.

The light-sensitive materials can, moreover, be protected from the harmful action of light by being coated with a protective layer, e.g., with a lacquer, containing at least one defined compound of the formula 1, or by being covered with materials, such as films, disks or sheets, which contain such protective agents against light rays. In these two cases, the amount of the added protective agent against light rays is advantageously -30 percent (relative to the protective-layer material) for protective layers of less than 0.01 mm. thickness, and 1-10 percent for protective layers of 0.01 to 0. 1 mm. thickness.

in the case of certain types of application, especially where a warm plastic granulate is powdered with protective substances, products are especially valuable which melt above the softening temperature of the particular polymer, and which nevertheless are sufficiently soluble in the melted polymer.

The new compounds of the general formula I can be obtained, for example, by the following reactions:

a. the compounds of the general formula in is reacted with approximately 3 equivalents of an alkylating agent.

The following are mentioned as alkylating agents: dialkyl sulfates such as, e.g. dimethyl sulfate or diethyl sulfate 1- bromoalkanes, l-chloroalkanes, 2-bromoalkanes or 2- chloroalkanes such as, e.g., l-bromoethane, l-chloropropane, Z-bromopropane, l-bromobutane, l-bromo-3,3-dimethylpropane, l-chloro-3,3-dimethylbutane, l-bromohexane, lbromododecane or l-bromooctadecane, benzyl chloride, benzyl bromide, alkenyl bromides or -chlorides such as, e.g., allyl chloride, allyl bromide, methallyl chloride or methallyl bromide.

The reaction is performed in the presence of acid acceptors such as, e.g., sodium carbonate, sodium hydroxide or potassium hydroxide, and in solvents such as, e.g., alcohols, ketones, dimethylacetamide or mixtures thereof with water, at temperatures of 20 l 50' C., preferably at 40- l 20 C., or

c. compounds of the general formula lc,

are rearranged by Fries displacement. This rearrangement cannot be used for the production of compounds of the general formula I, wherein X represents alkenyl.

The production of the compounds of the formula lb is performed, for example, by complete dealkylation of a compound of the formula Ia, wherein X denotes, e.g., an alkoxy group. Compounds of the formula la are produced, by a Friedel- Crafts reaction, from 1 mole of benzene-1,3,5-tricarboxylic acid chloride and approximately 3 moles of a resorcin-monoor di-alkyl ether.

Suitable as resorcin alkyl ethers are, e.g.: resorcin monomethyl ether, resorcin dimethyl ether, resorcin diethyl ether, resorcin monobutyl ether, resorcin dibutyl ether, resorcin monohexyl ether, resorcin dioctyl ether, resorcin didodecyl ether.

The reaction is performed in the presence of about 3 moles of a Friedel-Craft's catalyst such as, e.g., AlCl and in a solvent which is inert to the reaction components and to the applied reaction conditions, such as l,l,2,2-tetrachloroethane, chlorobenzene or nitrobenzene. There thereby occurs with the use of resorcin dialkyl ethers, particularly during heating of the reaction mixture to elevated temperatures, a usually very slight dealkylation of the alkoxy groups which are in 0- position to the carbonyl groups.

The compound I, wherein X represents hydrogen, is

produced by complete dealkylation of compounds of the formula ld,

QW n 0 0 OR OR i= OR wherein R represents lower alkyl, which can be obtained by alkaline condensation of o-alkoxy-w-formyl-acetophenones [Report 100, 2554-2560 i967), F.Eiden et al.

The following examples illustrate the invention,-whereby the temperatures are given in degrees Centigrade.

v 7 EXAMPLE 1 A. While stirring proceeds and cooling to -l0 internal temperature is maintained, 398 g. of trimesic acid chloride are firstly added in portions to 1800 ml. of tetrachloroethane followed by 618 g. of powdered commercial AlCl Into the obtained suspension are added dropwise at 5-l0, within 30 minutes and while stirring, 621 g. of resorcin dimethyl ether. After completion of the addition, the reaction mixture is heated, while being stirred, within one hour to 80 internal temperature, whereby initially complete solution of the reaction components occurs. Fromabout 70, the reaction mixture commences to become cloudy again and changes, as the reaction proceeds, into a coarse-grained suspension.

At about 80 internal temperature, an active splitting off of HCl and methyl chloride commences. The reaction is allowed to proceed for 1 hour with continued stirring and maintenance of the internal temperature whereupon the internal temperature is raised to 90 and thereaction completed at this temperature during a further hour.

After being cooled, the reaction mixture is decomposed with an ice water/hydrochloric acid mixture, heated then to 50-60 internal temperature and the solvent removed by steam distillation. The yellow reaction product solidifies upon cooling. After recrystallization from ethylene glycol monomethyl ether is obtained l,3,5-tris-(2'-hydroxy-4'- methoxy-benzoyl)-benzene having a melting point of l72l7 4. This substance is sufiiciently pure for further processing. Recrystallized from toluene, it is obtained in the form of faintly yellow crystals, M.P. l82-l 83;

A 336 nm; e 30000 B. 48 g. of powdered commercial AlCl, are added in portions at room temperature, while stirring proceeds, to 500 ml. of anhydrous benzene, whereupon are added, likewise in portions, 2 l .2 g. of the product produced under A. Within half an hour, the reaction mixture is refluxed to boiling, while beingstirred, and maintained for 3 hours at this temperature. After tion again extracted by shaking with distilled water. After drying of the solution, the solvent is removed, the reaction product taken up in toluene and purified by repeated treatment with fullers earth. After the solvent has been evaporated off, the product solidifies in a vitreous form. It is dissolved in toluene, the solution is applied to a silica gel column and ex-' tracted with toluene.

After concentrating the first fraction, l,3,5'tris-(2'-hydroxy-4-ethoxy-benzoyl)-benune is obtained which, after recrystallization from an isopropanol/benzene mixture, melts at 152.

x, 336 nm;; 31800.

EXAMPLE 3 48.6 g. of the tris-l,3,5-(2',4-dihydroxy-benzoyl)-benzene, produced according to example i B, are dissolved in 200 ml. of dimethylacetamide and to the solution are added 30 ml. of 30 percent sodium hydroxide solution and a spatula-tip of potassium iodide. While stirring is maintained, 1 12 g. of bromododecane are added at 60-65. After the addition is completed, the temperature is raised to 90l00 and held there for 6 hours. The reaction mixture is stirred into water, which has been acidified with hydrochloric acid, the reaction mixture taken up in chloroform and repeatedly extracted by shaking with distilled water. After drying of the organic phase, the solvent is evaporated off, the residue taken up in toluene and, in order to purify it, repeatedly treated in the hot state with fullers earth. After the solvent has been evaporated off, the initially viscous product partly crystallizes after standing for some time at room temperature. After recrystallization from hexane, l,3,5-tris-(2'-hydroxy-4'-dodecyloxy-benzoyl)- benzene is obtained which melts at 90-9l. A 336 nm; e 34000.

If, instead of l-bromododecane, the equimolecular amount of the alkylating agents are used which are given in table I, using otherwise the same procedure, then the compounds, listed in the table, are obtained.

TABLE I Alkylating agent Compound nm. tivity (a) l-bromoethane 1,3,5-tris-(2-hydroxy-4-ethoxy-benzoyl)benzene-.. 336 55.6 l-bromopropane... 1,3,5-trls-(2-hydroxy-4-propoxy-benzoyl)-benzene 336 51.4 2-bromopropane 1,3,5-tris-(2-hydroxy-4-isoprpoxy-benzoyl)Fbcnzene.. 336 61.3 l-chloropentane 1,3,5-tris-(2-hydroxy-4-pentoxy-benzoyl)-benzene 336 46.0 l-chloro-S,3-dimethybbutane. 1,3,5-tris-[2-hydr0xy-4-(3,3'-dlmethyl-butoxy)-benzoyl]-benzene 336 45.6 l-bromooctane i,3,5-tris-(2-hydr0xy-4'-octoxy-benzoyl)-benzene 336 37.5 l-chlorooctadecane 1,3,5-tris-(2-hydroxy-4-0ctadecyloxy-benzoy])-benzene 336 24.9 l-chloro-Z-methyl-propene 1,3,6-tris-[2-hydroxy-4-(2-methyl-propenoxy) -benzoyl]-benzene 337 48. 1 Benzyl chloride 1,3,5tris-(2'-hydroxy-4-benzyloxy-benzoyl)-benzene 336 44. 3 1,3,5-tris-(2-hydroxy-4-allyloxy-benzoyl) -benzene 336 51. 5

Allyl chloride;

being cooled, the reaction mixture is decomposed with an ice water/hydrochloric acid mixture and then subjected to steam distillation. The yellow fine-grained reaction product is filtered off, after cooling, washed thoroughly with water and dried.

After repeated recrystallization from a methanol/water mixture, and after drying, tris-l,3,5-(2', 4-dihydroxy-benzoyl)- benzene is obtained, which melts at 272-274.

A 329 nm; e 30500 EXAMPLE 2 12.1 g. of sodium hydroxide and 15.9 g. of sodium carbonate are dissolved in 200 ml. of water and to the solution are added 48.6 g. of the tris-l,3,5-(2',4'-dihydroxy-benzoyl)- benzene, as produced in example 1 B. While stirring proceeds, the temperature is raised to 70 and 46.2 g. of diethyl sulfate are added dropwise over 15 minutes. After the addition is completed, the temperature is raised to 80 and maintained there for 7 hours. After being cooled, the reaction mixture is stirred into water, slightly acidified, the blackish-brown reaction product taken up in chloroform and the chloroform solu- The absorptivity (a) is defined as follows:

EXAMPLE 4 A solution of 17.8 g. of o-methoxy-m-formylacetophenone in 100 ml. of methanol is added dropwise, within one hour at room temperature, to a solution of 1.4 g. of sodium methylate in 60 ml. of water and ml. of methanol. This reaction mixture is stirred for 24 hours at room temperature, whereby l,3,5-tris-(o-methoxybenzoyl)-benzene crystallizes out. This is recrystallized from alcohol and then melts at 156.

The demethylation of the 3 methoxyl groups of the obtained compound is performed by boiling in a solution of hydrobromic acid in glacial acetic acid. By this means is obtained l,3,S-tris-(o-hydroxy-benzoyi)-benzene which, after being recrystallized from ligroin, melts at 170.

A, =346 nm; e 15600 EXAMPLE 5 A solution of g. of acetyl cellulose having, on average. 2.5-acetoxy groups per glucose unit, and 0.075 g. of a UV-absorber, listed in the following table 11, in 85 g. of acetone is smeared on to a glass plate to form a film. The cellulose acetate films, obtained after evaporation of the acetone, are firstly dried at room temperature and then in an oven at Specimens of these 0.04 mm. thick UV-filters are exposed, in order to measure the fastness to light of the UV-absorbers, for 500 hours in the Fade-O-Meter and tested with respect to their residual UV-absorption. The obtained results are given in table ll.

TABLE II mixture of 343 g. of maieic acid anhydride and 428 g. of

tetrachlorophthalic acid anhydride is added in portions at to a mixture of 170 g. of ethylene glycol and 292 g. of diethyiene glycol. After expulsion of the air in the reaction vessel by nitrogen, the temperature is raised over one hour to 150, then over 9 hours to 210 and thereafter maintained at this level for a further hour. The mixture is then cooled to 180, the vessel is put under vacuum and the pressure slowly reduced to 100 Torr. These conditions are maintained until the acid number of the reaction mixture has fallen below 50.

100 g. of the thus obtained polyester are mixed with 50 g. of styrene and the mixture is polymerized under the aforementioned conditions.

Similar results are obtained if, instead of the tetrachlorophthalic acid, the equivalent amount of phthalic acid anhydride is used, although, in this case, the resulting polyester resin is not difficulty inflammable.

Absorption still present in percent of the original UV-absorption after exposure range, 300- No. UV-absorber 340 nm.

a 1,3,5-tnls-(2,4'-dihydroxy-benzoy1)-benzene 100 b- 1,3,5tris-(2-hydroxy-4-mthoxy-benzoyl)-benzene 96 c- 1,3,5tris-(2-hydroxy-4-ethoxy-benzoyl)-benzene 97 d 1,3,5-tris-(2-hydroxy-4-but0xy-benzoyl)-benzene 98 e 1,3,5-tris-[2-hydroxy4-(3",3-dimethylbutoxy) -benzoyl]-benzene 96 L 1,3,5-tris-(2-hydroxy-4-oetoxy-benzoyl) -benzene 99 g- 1,3,5-tris-(2-hydroxy-4-dodecy1oxy-benzoyl)-benzene 97 h 1,3,5-tris-[2-hydroxy-4-(2-methylpropenoxy) -benzoyl]-benzene 98 i. 1,3,5-tris-(2'-hydroxy-4-benzyloxy-benz0yl) -benzene j 1,3,5-tris(2-hydroxy-benzoyi)-benzene 91 EXAMPLE 6 Difficulty inflammable. liquid polyester resin is polymerized at 80", after addition of 0.25 percent by weight of a UV-absorber, given in table 11], with 1 percent by weight of benzoyl if, in the above described process, the styrene is replaced by methyl methacrylate, then plates are obtained which are, in themselves, less prone to browning and which, moreover, are more easily stabilized.

light but produced without the aforementioned UV-absorbers.

TABLE III Percent trans- Percent with 440 nm. transmission after 1,000 with 440 nm. hours Fade-O- No. UV-absorber before exposure Meter exposure None. 88 31 a 1,3,5-tris-(2,4dihydroxy-benzoyl)-benzene 88 3.0 b 1,3,5-tris-(2-hydroxy-4-ethoxy-benzoyl)-benzene 87 2. 1 c 1,3,5-tris-[2-hydroxy-i'(2-methylpropenoxy)-benzoyl]-benzone 86 1.5 d 1,3,5-tris-[2-hydroxy-4-(3,3-dimethylbutoxy)-benzoyll-benzene 88 2. 2

g 1,3,5-tris-(2-hydroxy-4'-benzyloxy-benzoyl)-i)enzene g;

y-benzoyl) -benzene EXAMPLE 7 100 parts of methacrylic acid methyl ester, 0.5 parts of a UV-absorber from table IV and 0.2 parts of lauroyl peroxide are mixed together and polymerized at a temperature of 50-70 in the form of plates of 2 mm. thickness.

As can be seen from the following table, such plates can be employed as US-filters.

peroxide, to form 2.5 mm. thick plates. The plates are afterwards cured at Plates produced in this manner and exposed to light exhibit appreciably less browning than plates similarly exposed to 60 The employed polyester resin was produced as follows: A-

TABLE IV Percent transmission of light 01 the wave lenght N o. UV-absorber 340 nm 430 nm None 86 02 a. tris-l,3,6-(2'-hydroxy-4 methoxybenzoyD- 2 512 b tris-1,3,5-(2 ,4-dihydroxy-benzoyl)-benzene 2 93 e. tris-l,3,5-(2'-hydroxy-4-lmtoxybenzoyl)-henze 2 R (1.- tris-l,3,5-[2-hydroxy-4-(3",3-(iimethylbutoxy)-benzoyl]-benzen 2 Q 1 0.. tris-l,3,5-(2-hydroxy-4-octoxyhenzoyl)Jmnzone H 1' trls-l,3,5-(2-hydroxy-4-(lodeeyloxy-hm1zoyl)-benzene n EXAMPLE 8 Films are produced in the usual manner on a two-roller mill from a mixture of: 100 parts of a suspension polyvinyl chloride (K-value 60), 2.5 parts of a dialkyl tin mercaptide stabilizer (Advastab 17 M of the Deutschen Advance Produktion Gmbl-i, Germany), 1.0 part of an epoxy stabilizer (Advaplast 39 of the aforementioned firm), f 1.0 part of a wax, employed as lubricant and processing auxiliary agent (Wax E of the firm Farbwerke Hoechst, Germany) and 0.2 parts of a UV-absorber from table V.

Specimens of these films are exposed for 2000 hours in the Xenotest exposure apparatus and tested with respect to discolorations.

The results are given in table Va.

TABLE Va Appearance of the exposed specimen Dark brown discolouration of the whole specimen.

Slightly yellowish.

UV-absorber Withoutv UV-absorber b 1,3,6-tris-(2-hydroxy-4-ethoxy- Commencement of benzoyl)-benzene. yellowing. c 1,3,5-tris-(2-hyd1oxy-4-dodecyloxy- Slightly yellowish at benzoyD-benzene. isolated places if, instead of the aforementioned mixture, the following recipe is used: 100 parts of suspension polyvinyl chloride (K-value 62), 1.2 parts of a barium-cadmium'soap (Mark WS of the S. A. Argus Chemical N.V., Belgium), 0.5 parts of an organic phosphite (Mark C of the above firm), 1.0 part of a wax (Wax'E of the Farbwerke Hoechst, Germany, and 0.2 parts of a UV-absorber from table Vb, with otherwise the same procedure, the results given in table 100 parts of polyethylene with a density of 0.9 l 7 are homogeneously mixed at 180 in the Brabender-Plastograph with 0.5 parts of a UV-absorber from table VI and 0.5 parts of 3-( 3 ,5 '-di-t.-butyl-4-hydroxy-phenyl )-propionic acidoctadecyl ester. The thus obtained mixture is pressed in a platen press at 165 to form 1 mm. thick plates.

After weathering, these plates exhibit, in the case, of bending around 90, appreciably less proneness to brittleness than plates without the addition of the additives in table Vl.

TABLE VI No. UV-A bsorber a trisl ,3,5-(2'-hydroxy-4'-propoxy-benzoyll-benzenc b trisl ,3 ,5-( 2 'hydroxy-4'-butoxy-benzoyl )-benzene c Iris-1,3 ,5-( 2-hydroxy-4 '-oetoxy-benzoyl )-benzene d trisl ,3,5-( 2'-hydroxy-4-octadecyloxy-benzoyl)- benzene if, instead of the aforementioned phenolic antioxidant, an

equal amount of 3,5-di-t.butyl-4-hydroxy-benzyl-di-octadecylphosphonate is used, similar results are obtained with otherwise the same procedure.

EXAMPLE l0 100 parts of polypropylene with a density of 0.90 are homogeneously mixed at 220 in the Brabender-Plastograph with 0.5 parts of a UV-absorber from table Vll, 0.2 parts of bis-(5-t.butyl-4-hydroxy-2-methyl-phenyl)-sulphide, 0.2 parts of dilauryl thiodipropionate and 0.2 parts of trioctadecyl phosphite. The thus obtained mixture is pressed in a platen press at 180 to form 1 mm. thick plates.

After weathering, these plates exhibit, in the case of bending around appreciably less proneness to brittleness than plates produced otherwise in the same manner, but without addition of the protective agents against light rays given in table Vll.

TABLE VII No. UV-Absorber a trisl ,3,5-( 2'-hydroxy4'-ethoxy-benzoyl )-benzeneb trisl ,3,5-( 2-hydroxy-4'-hexexy-benmyl)-benunc c trisl ,3,$-[2'-hydroXy-4-( 2"-methylpropenoxy benzoyll-benzene d trisi ,3,5-(2'-hydroxy-4'-dodecyloxy-benzoyl)- benzene e tris-l ,3,5-( 2-hydroxy-4'-benzyloxy-benzoyl benzene EXAMPLE 1 l parts of polystyrene granulate are mixed dry with 0.3 parts of a protective agent against light rays from table VIII and 0.1 parts of 2,4,6-tri-t.-butyl-phenol and the mixture is sprayed with an injection moulding machine to form 2 mm. thick plates.

The obtained plates are exposed for 1000 hours in the Xenotest apparatus and afterwards the yellowing of the plates is determined by means of the yellowing factor in the followmg manner:

AT(420)AT(680) whereby AT represents the transmission loss occurring during exposure with the wave-lengths 420 and 680 nm. and T(560) represents the transmission value in percent of the unexposed specimen in the case of 560 nm.

ing the following composition:

l5.0 parts by weight of cellulose acetate CELLlT F 900 (of the Firma Bayer in Leverkusen, Germany) with ca. 56 percent acetic acid content,

10.0 parts by weight of dimethyl glycol phthalate,

1.0 part by weight of 1,3,5-tris-(2'-hydroxy-4'-ethoxybenzoyl)-benzene, 5.0 parts by weight of methyl alcohol, 10.0 parts by weight of toluene and 50.0 parts by weight ofethylacetate.

The natural yellowing of the wood is retarded by this varnish.

EXAMPLE 13 A cosmetic protective agent against light rays is obtained as follows: parts of white ceresine wax 22 parts of white petrolatum 19.5 parts of white mineral oil, 15 parts of lanoline anhydrous 2 parts of 2,4,5-tris-(2, 4-dihydroxy-benzoyl)-benzene 36 parts of water 0.5 parts of perfume The ceresine, petrolatum and lanoline are melted together and the protective agent against light rays dissolved in the melt. The mineral oil is then added at 70 and, following this, the water is slowly stirred in at the same temperature. Stirring is continued until the temperature has fallen below 50, whereupon the perfume is added.

EXAMPLE 14 A sprayable cosmetic protective agent against light rays is obtained by dissolving in 80 parts of ethanol, parts of ricinic acid methyl ester, 10 parts of oleyl alcohol and one part of l,3,5-tris-(2'-hydroxy-4'-butoxy-benzoyl)-benzene. After addition of the commercial fluorine-containing propellants (e.g. Freon products of the firm Du Pont, USA), the solution can be sprayed from an aerosol container.

What we claim is:

1. Compounds of the general formula I,

l4 (|)H ()H C o 1; ll 0 X- X i @OH H. 2 two We... wi l wherein X represents hydrogen, hydroxyl, alkoxy having one to 22 carbon atoms, alkenyloxy having three to' 18 carbon atoms or benzyloxy which can be substituted by alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms or chlorine.

2. Compounds as claimed in claim 1, wherein X represents hydroxyl, alkoxy having one to 22 carbon atoms, alkenyloxy having three and four carbon atoms or benzyloxy.

3. Compounds as claimed in claim 1, wherein X represents hydroxyl, alkoxy having one to 22 carbon atoms or alkenyloxy having three and four carbon atoms.

4. Compounds as claimed in claim 1, wherein X represents alkoxy having four to 12 carbon atoms.-

5. A compound as claimed in claim 1 which is l,3,5-tris-(2', 4'-dihydroxy-benzoyl)-benzene.

6. A compound as claimed in claim I which is l,3,5-tris-(2'- hydroxy-4'-methoxy-benzoyl)-benzene.

7. A compound as claimed in claim 1 which is l,3,5-tris-(2- hydroxy-4-butoxy-benzoyl) benzene.

8. A compound as claimed in claim 1 which is l,3,5-tris-(2'- hydroxy-4'-octoxy-benzoyl)-benzene.

9. A compound as claimed in claim 1 which is l,3,5-tris-(2- hydroxy-4-dodecyloxy-benzoyl)-benzene.

* t t i 

2. Compounds as claimed in claim 1, wherein X represents hydroxyl, alkoxy having one to 22 carbon atoms, alkenyloxy having three and four carbon atoms or benzyloxy.
 3. Compounds as claimed in claim 1, wherein X represents hydroxyl, alkoxy having one to 22 carbon atoms or alkenyloxy having three and four carbon atoms.
 4. Compounds as claimed in claim 1, wherein X represents alkoxy having four to 12 carbon atoms.
 5. A compound as claimed in claim 1 which is 1,3,5-tris-(2'', 4''-dihydroxy-benzoyl)-benzene.
 6. A compound as claimed in claim 1 which is 1,3,5-tris-(2''-hydroxy-4''-methoxy-benzoyl)-benzene.
 7. A compound as claimed in claim 1 which is 1,3,5-tris-(2''-hydroxy-4''-butoxy-benzoyl)-benzene.
 8. A compound as claimed in claim 1 which is 1,3,5-tris-(2''-hydroxy-4''-octoxy-benzoyl)-benzene.
 9. A compound as claimed in claim 1 which is 1,3,5-tris-(2''-hydroxy-4''-dodecyloxy-benzoyl)-benzene. 